Direct observation of C - O reductive elimination from Pt(IV) [4]

Journal of the American Chemical Society

Volumn 121, Issue 1, 1999, Pages 252-253

  Williams, B Scott ^a   Holland, Andrew W ^a   Goldberg, Karen I ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CHEMICAL BOND; CHEMICAL REACTION; LETTER; STRUCTURE ANALYSIS; X RAY DIFFRACTION;

EID: 0033550529     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja982211y     Document Type: Letter

References (31)

1. Parshall, G. W.; Ittel, S. D. Homogeneous Catalysis: The Applications and Chemistry of Catalysis by Soluble Transition Metal Complexes, 2nd ed.; Wiley-Interscience: New York, 1992.
2. Shilov, A. E. Activation of Saturated Hydrocarbons by Transition Metal Complexes; D. Riedel: Dordrecht, The Netherlands, 1984.
3. Mechanistic support has been presented for the product forming step in Shilov's oxidations being nucleophilic attack at a Pt(IV) carbon group by an external heteroatom species. This reaction which results in C-X bond formation and generation of a Pt(II) species is sometimes classified as a reductive elimination. Luinstra, G. A.; Wang, L.; Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Organomet. Chem. 1995, 504, 75 and references therein.
4. Periana, R. A.; Taube, D. J.; Gamble, S.; Taube, H.; Satoh, T.; Fujii, H. Science 1998, 280, 560.
5. See: (a) Hartwig, J. F. Angew. Chem., Int. Ed. 1998, 37, 2046-2067 and references therein. (b) Widenhofer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 6504 and references therein. (c) Han, R.; Hillhouse, G. L. J. Am. Chem. Soc. 1998, 120, 7657 and references therein. (d) Komiya, S.; Akai, Y.; Tanaka, K.; Yamamoto, T.; Yamamoto, A. Organometallics 1985, 4, 1130.
6. See: (a) Hartwig, J. F. Angew. Chem., Int. Ed. 1998, 37, 2046-2067 and references therein. (b) Widenhofer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 6504 and references therein. (c) Han, R.; Hillhouse, G. L. J. Am. Chem. Soc. 1998, 120, 7657 and references therein. (d) Komiya, S.; Akai, Y.; Tanaka, K.; Yamamoto, T.; Yamamoto, A. Organometallics 1985, 4, 1130.
7. See: (a) Hartwig, J. F. Angew. Chem., Int. Ed. 1998, 37, 2046-2067 and references therein. (b) Widenhofer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 6504 and references therein. (c) Han, R.; Hillhouse, G. L. J. Am. Chem. Soc. 1998, 120, 7657 and references therein. (d) Komiya, S.; Akai, Y.; Tanaka, K.; Yamamoto, T.; Yamamoto, A. Organometallics 1985, 4, 1130.
8. See: (a) Hartwig, J. F. Angew. Chem., Int. Ed. 1998, 37, 2046-2067 and references therein. (b) Widenhofer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 6504 and references therein. (c) Han, R.; Hillhouse, G. L. J. Am. Chem. Soc. 1998, 120, 7657 and references therein. (d) Komiya, S.; Akai, Y.; Tanaka, K.; Yamamoto, T.; Yamamoto, A. Organometallics 1985, 4, 1130.
9. (a) Canty, A. J.; Jin, H. J. Organomet. Chem. 1998, 565, 135.
10. (b) Canty, A. J.; Jin, H.; Skelton, B. W.; White, A. H. Inorg. Chem. 1998, 37, 3975.
11. (a) Mann, G.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 13109.
12. (b) Thompson, J. S.; Randall, S. L.; Atwood, J. D. Organometallics 1991, 10, 3906.
13. 6 octahedral compound, has been reported. (a) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577. (b) Khin-Than, A.; Colpitts, D.; Ferguson, G.; Puddephatt, R. J. Organometallics 1988, 7, 1454.
14. 6 octahedral compound, has been reported. (a) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577. (b) Khin-Than, A.; Colpitts, D.; Ferguson, G.; Puddephatt, R. J. Organometallics 1988, 7, 1454.
15. 3) (6).
16. 2Pt), MW = 715.64, colorless rhombohedron, triclinic, space group = P1, a = 10.043(2) Å, b = 12.581(3) Å, c = 13.538-
17. 2) = 0.695.
18. Selected bond lengths(Å): Pt-C (trans to OAc) 2.079(7); Pt-C (cis to OAc) 2.087(7), 2.092(7); Pt-O 2.162(5); O-C 1.272(9); C=O 1.228(9). Select angles(deg): P-Pt-P 83.62(6); Pt-C-O 125.1(4); O-C=O 124.8-(7), O=C-C 119.1(7), O-C-C 116.1(7).
19. Swain, C. G.; Swain, M. S.; Powell, A. L.; Alunni, S. J. Am. Chem. Soc. 1983, 105, 502.
20. 5: Appleton, T. G.; Bennett, M. A. Inorg. Chem. 1978, 17, 738.
21. The reaction of 2 with HOAc has also been independently demonstrated.
22. -1).
23. 13 and DOAc further complicates the analysis. However, production of acetic acid during the reaction would be expected to cause a deviation from first-order behavior (see text) rather than simple variability between experiments.
24. 16 produced (Scheme 1).
25. 1H NMR for two half-lives, beyond which, the dynamic range of the NMR spectrometer hindered accurate data collection.
26. 3N and BuOAc occurs at a rate approximately an order of magnitude slower than the Pt(IV) reductive eliminations.
27. Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889 and references therein.
28. Hill, G. S.; Puddephatt, R. I. Organometallics 1997, 16, 4522 and references therein.
29. 31P NMR through the majority of the reaction were consistent with the final ratios. However, spectra taken at very early reaction times indicated higher amounts of C-C coupling. The low signal-to-noise ratios at early reaction times makes quantitation difficult. A trace amount of acid consumed during the reaction could be responsible for a higher initial C-C coupling rate as could a variable acetate concentration (see ref 17).
30. 2).
31. 3H has been employed successfully in a number of systems. See references in recent review article: Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2180.